TWI851751B - Pre-applied underfill material, laminate, semiconductor wafer with pre-applied underfill material layer, substrate for mounting semiconductor with pre-applied underfill material layer, and semiconductor device - Google Patents

Abstract

The present invention provides a film comprising a compound (A) containing at least one compound selected from the group consisting of maleimide compounds and citraconimide compounds, an organic peroxide (B) containing at least one compound selected from the group consisting of organic peroxides represented by a specific formula, and an imidazole compound (C) represented by a specific formula.

Description

Pre-coated bottom filling material, laminate, semiconductor wafer with pre-coated bottom filling material layer, semiconductor mounting substrate with pre-coated bottom filling material layer, and semiconductor device

The present invention relates to a film, a laminate using the film, a semiconductor wafer with a film layer, a semiconductor mounting substrate with a film layer, and a film. Specifically, the present invention relates to a film that is effective as a pre-coating bottom filling material.

In recent years, with the miniaturization and performance improvement of semiconductor devices, flip-chip mounting has attracted attention as a method of mounting a semiconductor chip (hereinafter sometimes referred to as a "chip") on a semiconductor mounting substrate (hereinafter sometimes referred to as a "substrate"). In flip-chip mounting, the general method is to fill the gap between the chip and the substrate with bottom fill material and harden it after the chip and the substrate are bonded. However, with the miniaturization and performance improvement of semiconductor devices, the electrodes arranged on the chip are being narrowed in pitch and the gaps between the electrodes are being narrowed. The long time of filling the bottom fill material has led to the deterioration of workability and the occurrence of poor filling such as leakage and non-filling, which has also become a problem. In response to this, some people have explored a method of supplying a pre-coated bottom fill material to a chip or substrate, and simultaneously bonding the chip and the substrate and filling the bottom fill material.

The bottom fill material is a component that is in direct contact with the chip and substrate, so the important properties required of the bottom fill material can be listed as follows: ensuring the most appropriate melt viscosity in the steps of manufacturing semiconductor devices, and suppressing the unfilled part of the bottom fill material between the chip and the substrate (hereinafter sometimes referred to as "gap") in the environment of manufacturing and using semiconductor devices.

Patent document 1 states: A pre-coated bottom fill material using a free radical polymerizable monomer in the main resin. Patent document 1 describes the blending of a silane coupling agent to improve adhesion to the chip.

Patent document 2 states: bottom filling material containing epoxy resin, imidazole compound, and maleimide compound.

Patent document 3 states: A pre-coated bottom filling material using epoxy compounds and flux components containing carboxyl groups, and mentions bonding.

Patent document 4 states: A resin composition having maleimide compounds, epoxy resins, and epoxy resin hardeners as essential components, and states: High adhesion can be obtained in the resin composition after thermal curing.

化合物、及無機填充材(C)之印刷配線基板用樹脂組成物的記載。 Patent document 5 discloses a thermosetting resin composition for forming an insulating layer in a printed wiring board, which contains a maleimide compound having a specific structure, a benzoic acid

Compound, and an inorganic filler (C) for a resin composition for a printed wiring board.

化合物作為硬化主劑，且含有酚系硬化劑之電子零件用黏接劑的記載。 Patent document 6 discloses a method for treating aliphatic epoxy compounds and benzoic acid

This document describes adhesives for electronic components that use a compound as the main curing agent and contain a phenolic curing agent.

Patent document 7 describes an adhesive composition containing a thermosetting compound, a polymer having a functional group that can react with the aforementioned thermosetting compound, and a thermosetting agent, with a melt viscosity at the bonding temperature of 10 Pa.s or more and 15000 Pa.s or less, a gelation time at the bonding temperature of 10 seconds or more, and a gelation time at 240°C of 1 second or more and 10 seconds or less.

Patent document 8 describes a method for manufacturing a semiconductor device using a sheet-shaped thermosetting resin composition.

Furthermore, when a chip and a substrate are joined via an easily oxidizable metal such as solder or copper, a flux component such as carboxylic acid is sometimes added to the pre-coated bottom fill material in order to remove the metal oxide film that becomes an obstacle to the joining from the joint and obtain a good metal joint.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2015-503220

[Patent Document 2] Japanese Patent Publication No. 2014-521754

[Patent Document 3] Japanese Patent Publication No. 2013-112730

[Patent Document 4] Japanese Patent Publication No. 2003-221443

[Patent Document 5] Japanese Patent Publication No. 2016-196548

[Patent Document 6] Japanese Patent Publication No. 2013-008800

[Patent Document 7] Japanese Patent Publication No. 2011-157529

[Patent Document 8] Japanese Patent Publication No. 2006-245242

However, generally speaking, free radical polymerizable monomers cure quickly, and the mobility of the bonding site of the mixed silane coupling agent is limited by the silanol groups on the chip surface and the main resin that has been polymerized before a sufficient number of bonds are formed. As a result, the pre-coated underfill material described in Patent Document 1 cannot ensure the most suitable melt viscosity, and cannot obtain sufficient adhesion and bonding with the chip and the substrate such as the printed wiring board, resulting in a tendency to generate voids. Furthermore, since the free radical polymerizable monomer cures quickly, the resin composition cures before filling the unevenness on the chip surface. Therefore, the pre-coated bottom filling material described in Patent Document 1 cannot fully obtain the anchor effect, which is effective in improving adhesion.

The material described in Patent Document 2 only acts on polyimide passivated films, so it has a narrow scope of application.

In the technology described in Patent Document 3, carboxyl-containing compounds and epoxy compounds will still react slightly even at room temperature, and the flux activity will decrease over time during storage. Therefore, the pre-coated bottom filling material described in Patent Document 3 has the problem of low bonding stability and lack of mass production.

In the technology described in Patent Document 4, the water absorption rate of maleimide resin is high, so there is a problem that the chip adhesion is greatly reduced after moisture absorption treatment. If the adhesion is insufficient, water will penetrate from the peeling interface and the insulation reliability will be greatly reduced. In addition, it is not easy to take into account both the adhesion to the chip and the adhesion to the printed wiring board with only maleimide resin.

Patent document 5 does not describe the activity of the flux, nor does it describe the composition of the flux. Therefore, the resin composition described in Patent document 5 will have the problem of not being able to achieve good metal bonding.

In Patent Document 6, epoxy compounds have high adhesion, but epoxy compounds also react with flux components, and there is a problem that the flux activity sufficient to obtain good metal bonding cannot be obtained.

The adhesive composition of Patent Document 7 contains a thermosetting agent with fluxing properties, but in the embodiment, epoxy compounds and epoxy-containing polymers are used, and since the two react at a temperature lower than the bonding temperature, it is not easy to obtain sufficient fluxing agent activity.

Patent document 8 also states that epoxy resin is suitable as the thermosetting resin contained in the thermosetting resin composition, but as mentioned above, epoxy compounds will also react with flux components and there will be a problem that the flux activity sufficient to obtain good metal bonding cannot be obtained.

The present invention is made in view of such a problem, and provides a film, a laminate, a semiconductor wafer with a thin film layer, a semiconductor mounting substrate with a thin film layer, and a semiconductor device with an excellent balance of storage stability, flexibility, flux activity, hardening, low voids, and melt viscosity.

The inventors of the present invention conducted in-depth research to solve the above-mentioned problems in the prior art and found that the above-mentioned problems can be solved by combining and using specific components, and even the present invention is completed.

That is, the present invention includes the following contents.

[1]

A film comprising: a compound (A) comprising at least one selected from the group consisting of maleimide compounds and oxadiazine compounds, an organic peroxide (B) comprising at least one selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2), and an imidazole compound (C) represented by formula (5).

In formula (1), R ¹ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

In formula (2), ^R2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and ^X1 represents a group represented by the following formula (3) or (4).

In formula (3), R ³ represents a hydrogen atom, a methyl group, or an ethyl group, R ⁴ represents an alkylene group having 1 to 3 carbon atoms, and R ⁵ represents a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms.

In formula (4), R ⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and X ² represents a group represented by the following general formulas (a) to (c).

In formula (c), ⁿ¹ represents an integer greater than or equal to 1 and less than or equal to 5.

In formula (5), ^R7 represents a methyl group or an ethyl group, ^R8 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and ^R9 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group.

[2]

The film as described in [1], wherein the compound (A) comprises a compound selected from 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimalimidyl, N,N'-1,4-phenylene dimalimidyl At least one of the group consisting of maleimide, N-phenylmaleimide, a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), a maleimide compound represented by the following formula (9), and a dimaleimide compound containing a constituent unit represented by the following formula (10) and maleimide groups at both ends.

In formula (6), ^R10 each independently represents a hydrogen atom or a methyl group, and ⁿ² represents an integer greater than 1.

In formula (7), n ³ represents an integer greater than or equal to 1 and less than or equal to 30.

In formula (8), R ¹¹ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ¹² each independently represents a hydrogen atom or a methyl group.

[Chemistry 10]

In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.

In formula (10), ^R14 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; ^R15 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; ^R16 each independently represents a hydrogen atom, a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; and ⁿ⁵ represents an integer of 1 to 10.

[3]

The film as described in [2], wherein the compound (A) comprises at least one selected from the group consisting of 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane, a maleimide compound represented by the above formula (6), a maleimide compound represented by the above formula (7), a maleimide compound represented by the above formula (8), a maleimide compound represented by the above formula (9), and a bismaleimide compound containing a constituent unit represented by the above formula (10) and maleimide groups at both ends.

[4]

A film as described in any one of [1] to [3], wherein the organic peroxide (B) comprises at least one selected from the group consisting of diisopropylbenzene peroxide, 4,4-di(tertiary butylperoxy)butyl valerate, di(2-tertiary butylperoxy isopropyl)benzene, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)-3-hexyne, and 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane.

[5]

A film as described in any one of [1] to [4], wherein the imidazole compound (C) is an imidazole compound represented by the following formula (11).

In formula (11), R ¹⁷ represents a methyl group or an ethyl group, R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and R ¹⁹ represents a hydrogen atom or a methyl group.

[6]

The film as described in [5], wherein the imidazole compound (C) is an imidazole compound represented by the following formula (12).

In formula (12), ^R20 represents a methyl group or an ethyl group, ^R21 represents a hydrogen atom, a methyl group, an ethyl group or a benzyl group, and ^R22 represents a hydrogen atom or a methyl group.

[7]

The film as described in [5] or [6], wherein the imidazole compound (C) comprises at least one selected from the group consisting of 1-benzyl-2-methylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole.

[8]

A film as described in any one of [1] to [7], wherein the content of the imidazole compound (C) is 10 parts by mass or less relative to 100 parts by mass of the compound (A).

[9]

化合物(D)。 The film as described in any one of [1] to [8] further contains benzo[13] represented by the following formula (14), the following formula (15), and the following formula (16):

Compound (D).

In formula (13), ^R23 each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, ^R24 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a 1-4 valent organic group represented by the following general formulae (d) to (w), and ⁿ⁵ represents an integer of 1 to 4.

In formula (14), ^R25 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; ^R26 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a 1-4 valent organic group represented by the following general formulae (d) to (r); and ⁿ⁶ represents an integer of 1 to 4.

In formula (15), R ²⁷ represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent.

In formula (16), R ²⁸ represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent.

[Chemistry 22]

In formulae (d) to (w), ^Ra represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and ^Rb represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.

[10]

化合物(D)包含選自於由下式(17)及下式(18)表示之化合物構成之群組中之至少1種。 The film as described in [9], wherein the benzo

The compound (D) comprises at least one selected from the group consisting of compounds represented by the following formula (17) and the following formula (18).

In formula (17), R ²⁹ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; R ³⁰ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; X ³ represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO ₂ -", a group represented by the formula "-CO-", an oxygen atom, or a single bond.

In formula (18), R ³¹ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; R ³² each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; X ⁴ represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO ₂ -", a group represented by the formula "-CO-", an oxygen atom, or a single bond.

In formula (19), Y is an alkylene group or a alkyl group having 6 or more and 30 or less carbon atoms and having an aromatic ring, and ⁿ⁷ represents an integer of 0 or more.

[11]

化合物(D)包含選自於由下式(20)表示之化合物、下式(21)表示之化合物、下式(22)表示之化合物、下式(23)表示之化合物、下式(24)表示之化合物、及下式(25)表示之化合物構成之群組中之至少1種。 The film as described in [9] or [10], wherein the benzo

Compound (D) includes at least one selected from the group consisting of a compound represented by the following formula (20), a compound represented by the following formula (21), a compound represented by the following formula (22), a compound represented by the following formula (23), a compound represented by the following formula (24), and a compound represented by the following formula (25).

[Chemistry 29]

In formula (22), R ³³ each independently represents a hydrogen atom or a carbon number 1 to 4 alkyl group.

[12]

化合物(D)的含量相對於前述化合物(A)100質量份，為5質量份以上且50質量份以下。 The film as described in any one of [9] to [11], wherein the benzo

The content of the compound (D) is 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the compound (A).

[13]

The film as described in any one of [1] to [12] further contains an acrylic compound (E).

[14]

The film as described in [13], wherein the content of the aforementioned acrylic compound (E) is 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the aforementioned compound (A).

[15]

The film described in any one of [1] to [14] further contains a flux component (F).

[16]

The film as described in [15], wherein the content of the flux component (F) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the compound (A).

[17]

The film described in any one of [1] to [16] further contains an inorganic filler (G).

[18]

A film as described in [17], wherein the average particle size of the inorganic filler (G) is less than 3 μm.

[19]

The film as described in [17] or [18], wherein the inorganic filler (G) comprises at least one selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide.

[20]

A film as described in any one of [17] to [19], wherein the content of the inorganic filler (G) is 300 parts by mass or less relative to 100 parts by mass of the compound (A).

[twenty one]

A film as described in any one of [1] to [20], further comprising hydroperoxide (H).

[twenty two]

The film as described in [21], wherein the content of the hydroperoxide (H) is 10 parts by mass or less relative to 100 parts by mass of the total amount of the compound (A).

[twenty three]

A film as described in any one of [1] to [22], having a thickness of not less than 10 μm and not more than 100 μm.

[twenty four]

A film as described in any one of [1] to [23] is used for a pre-coated bottom filling material.

[25]

A laminated body comprising: a supporting substrate, and a layer containing a thin film as described in any one of [1] to [24] laminated on the supporting substrate.

[26]

A semiconductor wafer with a thin film layer, comprising: a semiconductor wafer, and a stacked body as described in [25] stacked on the semiconductor wafer; and the layer containing the thin film is stacked on the semiconductor wafer.

[27]

A semiconductor mounting substrate with a thin film layer, comprising: a semiconductor mounting substrate, and a stacked body as described in [25] stacked on the semiconductor mounting substrate; and the thin film-containing layer is stacked on the semiconductor mounting substrate.

[28]

A semiconductor device comprising a semiconductor wafer with a thin film layer as described in [26] and/or a semiconductor mounting substrate with a thin film layer as described in [27].

According to the present invention, a film, a laminate, a semiconductor wafer with a thin film layer, a semiconductor mounting substrate with a thin film layer, and a semiconductor device with an excellent balance of storage stability, flexibility, flux activity, low voids, and melt viscosity can be provided.

The following is a description of the form used to implement the present invention (hereinafter referred to as "this embodiment"). In addition, the following embodiment is an example used to illustrate the present invention, and the present invention is not limited to this embodiment.

[Thin film]

The film of the present embodiment contains at least one compound (A) selected from the group consisting of maleimide compounds and oxadiazine compounds (hereinafter referred to as "compound (A)"), at least one organic peroxide (B) selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2) (hereinafter referred to as "organic peroxide (B)"), and an imidazole compound (C) represented by the following formula (5) (hereinafter referred to as "imidazole compound (C)"). Due to such a structure, the film of the present embodiment has an excellent balance of storage stability, flexibility, flux activity, curability, low voids, and melt viscosity. Due to such performance, the film of the present embodiment is suitable for use as a pre-coated bottom filling material used for flip-chip mounting of chips.

In formula (1), R ¹ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

In formula (2), ^R2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and ^X1 represents a group represented by the following formula (3) or (4).

In formula (3), R ³ represents a hydrogen atom, a methyl group, or an ethyl group, R ⁴ represents an alkylene group having 1 to 3 carbon atoms, and R ⁵ represents a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms.

In formula (4), R ⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and X ² represents a group represented by the following general formulas (a) to (c).

In formula (c), ⁿ¹ represents an integer greater than or equal to 1 and less than or equal to 5.

In formula (5), ^R7 represents a methyl group or an ethyl group, ^R8 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and ^R9 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group.

[Compound (A)]

From the viewpoint of insulation reliability and heat resistance, the film of this embodiment contains a compound (A) containing at least one selected from the group consisting of maleimide compounds and cisconamide compounds. There is no particular limitation if the compound (A) contains at least one selected from the group consisting of maleimide and cisconamide groups in the molecule. It is preferred that the compound (A) does not show reactivity with the flux component (F) described later. The compound (A) can be used alone or in combination of two or more.

Considering the fact that the acrylic compound (E) described later has excellent reactivity, insulation reliability, and heat resistance, the compound (A) in this embodiment preferably contains a maleimide compound.

The maleimide compound is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule. The maleimide compound can be used alone or in combination of two or more.

Specific examples of maleimide compounds include: N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenyl bismaleimide, 2,2-Bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfonium bismaleimide, 1,3-Bis(3-maleimidophenoxy)benzene, 1,3-Bis(4-maleimidophenoxy)benzene, polyphenylmethane maleimide, novolac maleimide compounds, biphenyl aralkyl maleimide compounds, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N '-1,3-phenylene dimalienyl, N,N'-1,4-phenylene dimalienyl, N-phenyl maleimide, maleimide compounds represented by the following formula (6), maleimide compounds represented by the following formula (7), maleimide compounds represented by the following formula (8), maleimide compounds represented by the following formula (9), and maleimide compounds containing a constituent unit represented by the following formula (10) and maleimide groups at both ends, etc., but not limited thereto. Compound (A) can also be contained in the film of the present embodiment in the form of a prepolymer obtained by polymerizing a maleimide compound and a prepolymer obtained by polymerizing a maleimide compound and other compounds such as an amine compound.

In formula (6), ^R10 each independently represents a hydrogen atom or a methyl group, and ⁿ² represents an integer greater than 1, preferably an integer greater than 1 and less than 10.

In formula (7), n ³ represents an integer greater than or equal to 1 and less than or equal to 30.

[Chemistry 42]

In formula (8), R ¹¹ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ¹² each independently represents a hydrogen atom or a methyl group.

In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10.

In formula (10), ^R14 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; ^R15 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; ^R16 each independently represents a hydrogen atom, a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; and ⁿ⁵ represents an integer of 1 to 10.

Among the above compounds, the compound (A) preferably includes a compound selected from 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimalimidamine, N,N'-1,4-phenylene dimalimidamine, N-phenylmaleimide, the maleimide compound represented by the above formula (6), the maleimide compound represented by the above formula (7), the maleimide compound represented by the above formula (8), the maleimide compound represented by the above formula (9), The maleimide compound represented by the above formula (6), the maleimide compound represented by the above formula (7), the maleimide compound represented by the above formula (8), the maleimide compound represented by the above formula (9), and the bismaleimide compound represented by the above formula (10), and the maleimide group. In addition, compound (A) is more preferably a maleimide compound represented by the above formula (9), and more preferably a maleimide compound represented by 2,2-bis[4-(4-maleimide-phenoxy)phenyl]propane, a maleimide compound represented by formula (7), a maleimide compound represented by formula (8), and a maleimide compound represented by formula (9), from the viewpoint of maintaining good storage stability, flexibility, flux activity, hardening property, and low voids, and especially improving melt viscosity.

As the maleimide compound, commercial products may be used. For example, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane may include BMI-80 (trade name) manufactured by Yamato Chemical Industries, Ltd. For example, the maleimide compound represented by formula (6) may include BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. For example, the maleimide compound represented by formula (7) may include BMI-1000P (trade name, n 3 = 14 (average) in formula (7)) manufactured by K.I Chemicals Co., Ltd., BMI-650P (trade name, n ₃ = 9 (average) in formula (7)) manufactured by K.I Chemicals Co., Ltd., and BMI-700P (trade name, n ₃ = 10 (average) in formula (7)) manufactured by K.I Chemicals Co., Ltd. BMI-250P (trade name, n ₃ = 3 to 8 (average) in formula (7)) manufactured by K.I Chemical Co., Ltd., CUA-4 (trade name, n ₃ = 1 in formula (7)) manufactured by K.I Chemical Co., Ltd., etc. For example, the maleimide compound represented by formula (8) includes BMI-70 (trade name; bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane) manufactured by K.I Chemical Co., Ltd. For example, MIR-3000-70MT (trade name, a mixture in which all R ¹³ in formula (9) are hydrogen atoms and n ⁴ is 1 to 10) manufactured by Nippon Kayaku Co., Ltd. Examples of maleimide compounds containing a constituent unit represented by formula (10) and maleimide groups at both ends include MIZ-001 (trade name) manufactured by Nippon Kayaku Co., Ltd.

The bisconimide compound is not particularly limited, and examples thereof include o-phenylenediconimide, m-phenylenediconimide, p-phenylenediconimide, 4,4-diphenylmethanediconimide, 2,2-bis[4-(4-coniminophenoxy)phenyl]propane, bis(3,5-dimethyl-4-coniminophenyl)methane, bis(3-ethyl-5-methyl-4-coniminophenyl)methane, bis(3,5-diethyl-4-coniminophenyl)methane, 1,3-diphenylenebis(xylenyl)bis(xylenyl)imide, N-[3-bis(trimethylsilyl)amino-1-propyl]xylenylimide, N-[3-bis(triethylsilyl)amino-1-propyl]xylenylimide, N-[3-bis(triphenylsilyl)amino-1-propyl]xylenylimide, N,N'-(m-xylylene)bis(xylenyl)imide, N-[3-(methylenesuccinimidylmethyl)benzylxylenylimide. The xylenylimide compound may be used alone or in combination of two or more.

In the film of this embodiment, the content of compound (A) is not particularly limited. From the perspective of ensuring the insulation reliability and heat resistance of the package after installation, the content of compound (A) in the film is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 50% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less.

[Organic peroxide (B)]

From the perspective of providing curability during installation, the film of this embodiment contains at least one organic peroxide (B) selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2). The organic peroxide (B) can be used alone or in combination of two or more.

[Chemistry 45]

In formula (1), R ¹ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

In formula (2), ^R2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and ^X1 represents a group represented by the following formula (3) or (4).

In formula (3), R ³ represents a hydrogen atom, a methyl group, or an ethyl group, R ⁴ represents an alkylene group having 1 to 3 carbon atoms, and R ⁵ represents a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms.

In formula (4), R ⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and X ² represents a group represented by the following general formulas (a) to (c).

In formula (c), ⁿ¹ represents an integer greater than or equal to 1 and less than or equal to 5.

In this embodiment, considering the solubility in organic solvents and the viewpoint of suppressing volatility or thermal decomposition during film production, the organic peroxide (B) preferably contains at least one selected from the group consisting of diisopropylbenzene peroxide, 4,4-di(tertiary butylperoxy) valerate, di(2-tertiary butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)-3-hexyne, and 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane.

In the film of this embodiment, the content of the organic peroxide (B) is not particularly limited. From the perspective of reducing the volatile amount during installation, it is preferably contained in an amount of 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the compound (A).

[Imidazole compound (C)]

From the perspective of providing curability during installation, the film of this embodiment contains an imidazole compound (C) represented by the following formula (5). The imidazole compound (C) can be used alone or in combination of two or more.

In formula (5), ^R7 represents a methyl group or an ethyl group, ^R8 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and ^R9 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group.

In this embodiment, considering the solubility in organic solvents and the reduction of volatility during installation, the imidazole compound (C) is preferably an imidazole compound represented by the following formula (11).

[Chemistry 51]

In formula (11), R ¹⁷ represents a methyl group or an ethyl group, R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and R ¹⁹ represents a hydrogen atom or a methyl group.

In this embodiment, from the perspective of ensuring molecular mobility during packaging, the imidazole compound (C) is preferably an imidazole compound represented by the following formula (12).

In formula (12), ^R20 represents a methyl group or an ethyl group, ^R21 represents a hydrogen atom, a methyl group, an ethyl group or a benzyl group, and ^R22 represents a hydrogen atom or a methyl group.

In this embodiment, considering both excellent flux activity and solubility in organic solvents, the imidazole compound (C) preferably includes at least one selected from the group consisting of 1-benzyl-2-methylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole.

In the film of this embodiment, the content of the imidazole compound (C) is not particularly limited. Considering the storage stability of the varnish and the curability during installation, it is preferably contained in an amount of 10 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the compound (A).

化合物(D)] [Benzo

Compound (D)]

化合物(D)。苯并

化合物若具有

環作為基本骨架，則無特別限制。本實施形態中，苯并

化合物也包含萘并

化合物等具有多環

骨架之化合物。本實施形態中，苯并

化合物(D)可單獨使用1種或混合使用2種以上。本實施形態中，苯并

化合物(D)宜為下式(13)、下式(14)、下式(15)、及下式(16)表示者。 The film of this embodiment may contain benzophenone from the viewpoint of imparting adhesion.

Compound (D). Benzo

If the compound has

There is no particular limitation on the basic skeleton of benzophenone.

Compounds also include naphthoxy

Compounds with polycyclic

In this embodiment, benzo

The compound (D) may be used alone or in combination of two or more.

The compound (D) is preferably represented by the following formula (13), the following formula (14), the following formula (15), or the following formula (16).

In formula (13), ^R23 each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, ^R24 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a 1-4 valent organic group represented by the following general formulae (d) to (w), and ⁿ⁵ represents an integer of 1 to 4.

In formula (14), ^R25 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; ^R26 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a 1-4 valent organic group represented by the following general formulae (d) to (r); and ⁿ⁶ represents an integer of 1 to 4.

In formula (15), R ²⁷ represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent.

In the formula (16), R ²⁸ represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent.

[Chemistry 61]

In formulae (d) to (w), ^Ra represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and ^Rb represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.

化合物(D)宜含有選自於由下式(17)及下式(18)表示之化合物構成之群組中之至少1種。 In this embodiment, considering the flame retardancy and heat resistance, benzo

The compound (D) preferably contains at least one selected from the group consisting of compounds represented by the following formula (17) and the following formula (18).

In formula (17), R ²⁹ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; R ³⁰ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; X ³ represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO ₂ -", a group represented by the formula "-CO-", an oxygen atom, or a single bond.

In formula (18), R ³¹ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; R ³² each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; X ⁴ represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO ₂ -", a group represented by the formula "-CO-", an oxygen atom, or a single bond.

In formula (19), Y is an alkylene group or a alkyl group having 6 or more and 30 or less carbon atoms and having an aromatic ring, and ⁿ⁷ represents an integer of 0 or more, preferably an integer of 0 or more and 5 or less.

化合物(D)宜包含選自於由下式(20)表示之化合物、下式(21)表示之化合物、下式(22)表示之化合物、下式(23)表示之化合物、下式(24)表示之化合物、及下式(25)表示之化合物構成之群組中之至少1種。 In this embodiment, from the viewpoint of solubility in organic solvents, benzo

Compound (D) preferably comprises at least one selected from the group consisting of a compound represented by the following formula (20), a compound represented by the following formula (21), a compound represented by the following formula (22), a compound represented by the following formula (23), a compound represented by the following formula (24), and a compound represented by the following formula (25).

[Chemistry 68]

In formula (22), R ³³ each independently represents a hydrogen atom or a carbon number 1 to 4 alkyl group.

化合物(D)中也可含有由單體聚合而生成的寡聚物等。 In addition, in this embodiment, benzo

The compound (D) may contain oligomers produced by polymerization of monomers.

化合物(D)的含量並無特別限制，考慮兼顧薄膜的黏接性及可撓性之觀點，相對於化合物(A)100質量份，宜含有5質量份以上且60質量份以下，含有10質量份以上且55質量份以下更佳，含有15質量份以上且50質量份以下再更佳。 In the film of this embodiment, benzo

The content of compound (D) is not particularly limited. From the viewpoint of both the adhesion and flexibility of the film, the content is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 55 parts by mass or less, and even more preferably 15 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of compound (A).

[Propylene compounds (E)]

From the viewpoint of imparting adhesion and hardening during installation, the film of this embodiment may also contain an acryl compound (E). There is no particular limitation on the acryl compound (E) as long as it contains an acryl group. In this embodiment, the acryl compound (E) may be used alone or in combination of two or more. In this embodiment, the acryl compound (E) preferably contains a constituent unit represented by the following formula (26) at the end of the molecule.

In formula (26), -* represents an atomic bond and is bonded to the main chain of the polymer.

The acryl compound (E) contains a highly reactive acryl group at the end, so the acryl groups react easily with each other, and the maleimide group and the octanoic acid imide group react with the acryl group during the curing process. Therefore, the crosslinking density of the obtained cured product is increased, low voids can be obtained, and the heat resistance (glass transition temperature) is improved. In addition, since it has a polar group, the chip adhesion of the adherend such as the chip and the substrate and the bottom filling material is also improved.

There is no particular limitation if the main chain polymer of the acrylic compound (E) contains alkenyl and hydroxyl groups.

There is no particular limitation on the alkenyl group, and examples thereof include vinyl, (meth)allyl, propenyl, butenyl, and hexenyl. Among them, propenyl is preferred.

The polymer is not particularly limited, and examples thereof include: bisphenol A, tetramethylbisphenol A, diallylbisphenol A, biphenol, bisphenol F, diallylbisphenol F, triphenylmethane-type phenol, tetraphenol, novolac-type phenol, cresol novolac resin, phenol having a biphenyl aralkyl skeleton (biphenyl-type phenol), and other polymers having alkenyl groups on the phenol ring. These polymers may also have substituents. Moreover, these polymers may be used alone or in combination of two or more.

Such substituents include: halogen atoms, and linear, branched, or cyclic hydrocarbon groups. In linear, branched, or cyclic hydrocarbon groups, as substituents, it is preferable to have an alkenyl group. The alkenyl group is as described above.

Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, etc.

There is no particular limitation on the linear or branched alkyl groups, and examples thereof include: methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, isobutyl, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohexyl, dihexyl, and tertiary hexyl.

The cyclic alkyl group is not particularly limited, and examples thereof include aliphatic cyclic alkyl groups and aromatic alkyl groups. Examples of aliphatic cyclic alkyl groups include monocyclic aliphatic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic alkyl groups such as bicyclo[2.2.2]octyl, tricyclo[5.2.1.0 ^2,6 ]decyl, tricyclo[3.3.1.1 ^3,7 ]decyl, tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodecyl, and adamantyl. Examples of the aromatic hydrocarbon group include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

The acrylic compound (E) is not particularly limited. From the perspective of preventing voids caused by the volatility of the acrylic compound (E) during flip chip mounting, the mass average molecular weight of the acrylic compound (E) is preferably 300 or more and 10,000 or less, more preferably 400 or more and 7,000 or less, and even more preferably 1000 or more and 3000 or less, as measured by polystyrene conversion using gel permeation chromatography (GPC).

The acryl compound (E) preferably includes a resin represented by the following formula (26-1) in which more than 20% of the alkenyl groups in the molecule are acryl groups. If the film of this embodiment contains such an acryl compound (E), excellent heat resistance can be obtained.

In formula (26-1), W each independently represents a alkyl group having 6 to 15 carbon atoms which may have a substituent. U each independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. n ¹ represents a repeating number, and its average value is a real number of 1 to 20.

In formula (26-1), W each independently represents a alkyl group having 6 to 15 carbon atoms which may have a substituent. The substituent in W preferably contains an aromatic ring. In this case, the propenyl compound (E) is preferably a resin represented by formula (26-2) described below, in which at least 20% of the alkenyl groups in the molecule are propenyl groups.

In addition, W in formula (26-1) is preferably an aromatic alkyl group, and more preferably an aromatic alkyl group having 10 to 15 carbon atoms. W is not particularly limited, and the following structures can be cited as examples. These structures can be one or two or more structures can be appropriately combined.

Among them, from the viewpoint of heat resistance, W preferably has an alkyl-type biphenyl skeleton.

In formula (26-1), more than 20% of the alkenyl groups in the molecule are acryl groups, which means that more than 20% of the total of U and terminal acryl groups are acryl groups. In formula (26-1), more than 40% of the alkenyl groups in the molecule are acryl groups, and more than 60% are acryl groups. There is no particular upper limit, which is 100%. If the alkenyl groups in the molecule fall within the above range, excellent curability can be obtained.

In formula (26-1), U other than the propenyl group independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. Examples of alkenyl groups having 2 to 6 carbon atoms include vinyl, (meth)allyl, butenyl, and hexenyl. From the perspective of appropriately controlling the curability, U other than the propenyl group is preferably a hydrogen atom.

In formula (26-1), ⁿ¹ represents a repetition number, and its average value is a real number of 1 to 20. From the viewpoint of appropriately controlling the hardenability, ⁿ¹ preferably has an average value of 1 to 10, and more preferably has an average value of 1 to 6.

When W in formula (26-1) contains an aromatic ring as a substituent, the propenyl compound (E) is preferably a resin represented by the following formula (26-2) in which 20% or more of the alkenyl groups in the molecule are propenyl groups.

In formula (26-2), Y each independently represents a alkyl group having 1 to 6 carbon atoms. X each independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. ⁿ² represents a repeating number, and its average value is a real number of 1 to 20.

In formula (26-2), Y each independently represents a trivalent alkyl group with 1 to 6 carbon atoms. Y is a structure in which a hydrogen atom in a divalent alkyl group with 1 to 6 carbon atoms is substituted by a phenol ring having an alkenyl group. Y is not particularly limited and is preferably a trivalent alkyl group with 1 to 6 carbon atoms in a linear, branched or cyclic form.

The linear hydrocarbon group is not particularly limited, and examples thereof include methylene, ethylene, propylene, butylene, pentylene, and hexylene. Examples of branched hydrocarbon groups include alkylmethylene groups such as -C( _CH3 ) _2- , -CH( _CH3 )-, -CH( _{CH2CH3 )} -, -C( _CH3 )( _CH2CH3 ) _{-, -C(CH3)(CH2CH2CH3 ) -} , and -C( _{CH2CH3 ) 2-} ; and alkylethylene groups such as -CH( _{CH3 ) CH2- ,} -CH( _CH3 )CH( _CH3 )-, -C( _CH3 ) _{2CH2- ,} -CH( _CH2CH3 ) _CH2- , _and -C( _{CH2CH3 ) 2} - _CH2- .

There is no particular limitation on the cyclic hydrocarbon group, and examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene.

These hydroxyl groups may be one type or two or more types may be appropriately combined.

Among them, Y is preferably a methine group from the viewpoint of obtaining good compatibility with other resins such as the organic peroxide (B) described later.

In formula (26-2), more than 20% of the alkenyl groups in the molecule are acryl groups, which means that more than 20% of the total of X and the terminal acryl groups are acryl groups. In formula (26-2), more than 40% of the alkenyl groups in the molecule are acryl groups, and more than 60% are acryl groups. The upper limit is not particularly limited and is 100. If the alkenyl groups in the molecule fall within the above range, excellent curability can be obtained.

In formula (26-2), X other than the propenyl group independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. The alkenyl group having 2 to 6 carbon atoms is as described above. From the perspective of appropriately controlling the curability, X other than the propenyl group is preferably a hydrogen atom.

In formula (26-2), n ² represents a repetition number, and its average value is a real number of 1 to 20. From the viewpoint of appropriately controlling the hardenability, n ² preferably has an average value of 1 to 10, and more preferably has an average value of 1 to 6.

The method for producing the propenyl compound (E) represented by formula (26-1) or formula (26-2) of this embodiment is not particularly limited, and it can be produced using a known method.

The manufacturing method may include, for example, a method using a phenolic resin as a raw material. The phenolic resin is not particularly limited, and may include: bisphenol A, tetramethylbisphenol A, diallylbisphenol A, biphenol, bisphenol F, diallylbisphenol F, triphenylmethane-type phenol, tetraphenol, novolac-type phenol, cresol novolac resin, phenol having a biphenyl aralkyl skeleton (biphenyl-type phenol), and phenol having a triphenylmethane skeleton (triphenylmethane-type phenol).

The production method can be obtained by allylating the hydroxyl groups in these phenolic resins to synthesize allyl ethers, and then subjecting the obtained allyl ether groups to a transfer reaction to propenyl ether groups. Alternatively, the obtained allyl ether groups can be subjected to a Claisen transfer reaction to obtain allylated phenol, and then subjecting the allyl groups to a transfer reaction to propenyl groups according to a known method to obtain the product.

The propenyl compound (E) is preferably a propenyl-containing resin having a structure represented by the following formula (26-3) and a propenyl-containing resin having a structure represented by the following formula (26-4). Such propenyl compounds (E) may also be commercially available products. For example, BPN01-S (trade name, mass average molecular weight: 1830) manufactured by Qun Rong Chemical Industries, Ltd. may be cited as a propenyl-containing resin having a structure represented by the following formula (26-3), and TPMP01 (trade name, mass average molecular weight: 2371) manufactured by Qun Rong Chemical Industries, Ltd. may be cited as a propenyl-containing resin having a structure represented by the following formula (26-4).

The above formula (26-3) is a mixture in which n ¹¹ is 1 to 10.

Formula (26-4) is a mixture in which n ¹² is 1 to 10.

In the film of this embodiment, the content of the acrylic compound (E) is not particularly limited. Considering the flexibility and adhesion of the film, it is preferably contained in an amount of 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A).

[Flux component (F)]

In order to make the flux active in flip chip mounting, the film of this embodiment preferably contains a flux component (F). There is no particular limitation if the flux component (F) is an organic compound having one or more acidic sites in the molecule. The acidic sites are preferably phosphate groups, phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups. In semiconductor devices using the film of this embodiment as a pre-coated bottom filling material, phenolic hydroxyl groups or carboxyl groups are more preferred from the perspective of more effectively preventing the migration and corrosion of metals such as solder and copper constituting the joint. The flux component (F) can be used alone or in combination of two or more.

There is no particular restriction on the flux component (F). In order to fully remove the oxide film at the joint, the acid dissociation constant pKa is preferably 3.8 or more and 15.0 or less. Considering the storage stability of the varnish and resin laminate and the flux activity, it is more preferably 4.0 or more and 14.0 or less.

The molecular weight of the flux component (F) in the film of this embodiment is not particularly limited. Considering the viewpoint of preventing the flux component (F) from volatilizing before the flux activity is exhibited in flip chip mounting, that is, preventing the flux component (F) from volatilizing before the oxide film of the joint is removed, the molecular weight is preferably 200 or more, preferably 250 or more. In order to have mobility as an acid and obtain sufficient flux activity, the molecular weight is preferably 8000 or less, preferably 1000 or less, and even more preferably 500 or less.

The flux component (F) is not particularly limited, and examples thereof include: abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, pimaric acid, palustric acid, bisphenolic acid, dihydroabietic acid, tetrahydroabietic acid, rosin-modified maleic acid resin and other rosin-modified maleic acid resins, N,N'-bis(2-hydroxybenzylidene)-1,2-propanediamine, N,N'-bis(2-hydroxybenzylidene)-1,3-propanediamine, and phenolphthalin. These flux components (F) are ideal from the perspective of excellent solvent solubility and storage stability.

Among them, dehydrorosinic acid, bisphenol acid, dihydrorosinic acid, tetrahydrorosinic acid, rosin-modified maleic acid resins, N,N'-bis(2-hydroxybenzylidene)-1,2-propanediamine, and N,N'-bis(2-hydroxybenzylidene)-1,3-propanediamine are more preferred from the viewpoint of preventing deactivation by compound (A). Dehydrorosinic acid, dihydrorosinic acid, rosin-modified maleic acid resin and other rosin-modified resins, N,N'-bis(2-hydroxybenzylidene)-1,2-propanediamine, and N,N'-bis(2-hydroxybenzylidene)-1,3-propanediamine have low reactivity and almost do not cause reaction with the compound (A) of this embodiment and the organic peroxide (B) of this embodiment, and are more ideal from the perspective of maintaining sufficient flux activity required for removing oxide films.

The flux component (F) may also be a commercially available one. An example of a rosin-modified maleic acid resin is MALKYD No. 32 (produced by Arakawa Chemical Industries, Ltd.), but the invention is not limited thereto.

In the film of this embodiment, the content of the flux component (F) is not particularly limited. Considering the insulation reliability and ensuring sufficient flux activity during installation, it is preferably contained in an amount of 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 65 parts by mass or less, and even more preferably 15 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the compound (A).

[Inorganic filler (G)]

In order to improve the flame retardancy, improve the thermal conductivity, and reduce the thermal expansion rate, the film of this embodiment should preferably contain an inorganic filler (G). By using an inorganic filler, the flame retardancy and thermal conductivity of the film can be improved and the thermal expansion rate can be reduced.

There is no particular restriction on the average particle size of the inorganic filler (G). Considering that the film of this embodiment is used as a pre-coated bottom filling material, it is preferably less than 3 μm, and more preferably less than 1 μm, in view of the narrow pitch of the electrodes arranged on the chip and the narrow gap between the electrodes. The lower limit of the average particle size is not particularly limited, for example, it is 10 nm. In addition, in this embodiment, the "average particle size" of the inorganic filler (G) means the median particle size of the inorganic filler (G). Here, the median particle size means that when the particle size distribution of the powder is divided into two sides based on a certain particle size, the volume of the particles on the larger particle size side and the volume of the particles on the smaller particle size side each account for 50% of the total powder. The average particle size (median particle size) of the inorganic filler (G) is measured using the wet laser diffraction-scattering method.

The inorganic filler (G) is not particularly limited, and examples thereof include: silica such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum compounds such as boehmite, aluminum hydroxide, aluminum oxide, and aluminum nitride; magnesium compounds such as magnesium oxide and magnesium hydroxide; calcium compounds such as calcium carbonate and calcium sulfate; molybdenum compounds such as molybdenum oxide and zinc molybdate; boron nitride; barium sulfate; talc such as natural talc and calcined talc; mica; glasses such as short fiber-shaped glass, spherical glass, and glass powder (such as E glass, T glass, D glass). Furthermore, when the thin film of the present embodiment is to be endowed with conductivity or anisotropic conductivity, the inorganic filler (G) may also be metal particles such as gold, silver, nickel, copper, tin alloy, and palladium.

Among them, from the viewpoint of improving the flame retardancy and reducing the thermal expansion rate of the film of the present embodiment, the inorganic filler (G) preferably includes at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, and silica, aluminum oxide, and boron nitride are more preferred, and silica is even more preferred. Examples of silicon dioxide include: SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Co., Ltd.; 0.3μm SX-CM1 (trade name), 0.3μm SX-EM1 (trade name), 0.3μm SV-EM1 (trade name), SC1050-MLQ (trade name), SC2050-MNU (trade name), SC2050-MTX (trade name), 2.2μm SC6103-SQ (trade name), SE2053-SQ (trade name), Y50SZ-AM1 (trade name), YA050C-MJE (trade name), YA050C-MJF (trade name), and YA050C-MJA (trade name) manufactured by Admatechs Co., Ltd.

These inorganic fillers (G) may be used alone or in combination of two or more.

Inorganic fillers (G) may also be those that have been surface treated with a silane coupling agent.

The silane coupling agent is not particularly limited if it is a silane coupling agent commonly used for surface treatment of inorganic substances. Examples include: vinyl silane-based silane coupling agents such as vinyl trimethoxy silane and γ-methacryloyloxypropyl trimethoxy silane; phenyl amino silane-based silane coupling agents such as N-phenyl-3-aminopropyl trimethoxy silane; phenyl silane-based silane coupling agents such as trimethoxyphenyl silane; and imidazole silane-based silane coupling agents. These silane coupling agents may be used alone or in combination of two or more.

In the film of this embodiment, the content of the inorganic filler (G) is not particularly limited. Considering the improvement of the flame retardancy of the film and the reduction of the thermal expansion rate, it is preferably contained in an amount of 300 parts by mass or less, more preferably 20 parts by mass or more and 300 parts by mass or less, and even more preferably 50 parts by mass or more and 250 parts by mass or less, relative to 100 parts by mass of the compound (A).

[Hydrogen peroxide (H)]

From the perspective of imparting hardening properties during installation, the film of this embodiment may also contain hydroperoxide (H). Hydroperoxide (H) is not particularly limited as long as the hydrogen atom of hydrogen peroxide is substituted by an organic group. In this embodiment, hydroperoxide (H) may be used alone or in combination of two or more.

Hydroperoxides (H) include, for example, hydroperoxides represented by the following formula (h1), hydroperoxides represented by the following formula (h2), and hydroperoxides represented by the following formula (h3).

In formula (h1), R ¹⁴ each independently represents a hydrogen atom or a methyl group, and R ¹⁵ represents a hydrogen atom, a methyl group, an isopropyl group, or a tertiary butyl group.

In formula (h2), R ¹⁶ each independently represents a hydrogen atom or a methyl group, and R ¹⁷ represents a hydrogen atom, a methyl group, an isopropyl group, or a tertiary butyl group.

In formula (h3), R ¹⁸ each independently represents a hydrogen atom or a methyl group, R ¹⁹ each independently represents a hydrogen atom or a methyl group, and R ²⁰ represents a hydrogen atom or a methyl group.

The molecular weight of the hydroperoxide (H) is not particularly limited. From the perspective of reducing the volatile amount during installation, it is preferably 100 or more, and more preferably 130 or more. From the same perspective, the hydroperoxide (H) preferably includes at least one selected from the group consisting of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and tert-amyl hydroperoxide.

In the film of this embodiment, the content of hydroperoxide (H) is not particularly limited. Considering the curability during installation and the reduction of volatile matter, it is preferably contained in an amount of 10 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of compound (A).

[Other ingredients]

化合物(D)、丙烯基化合物(E)、助熔劑成分(F)、無機填充材(G)及氫過氧化物(H)之外，也可含有1種或2種以上之其它成分。 The film of this embodiment contains compound (A), organic peroxide (B), imidazole compound (C), benzo

In addition to the compound (D), the acrylic compound (E), the flux component (F), the inorganic filler (G) and the hydroperoxide (H), one or more other components may be contained.

化合物(D)、丙烯基化合物(E)及助熔劑成分(F)除外之聚醯亞胺、聚醯胺醯亞胺、聚苯乙烯、聚烯烴、苯乙烯-丁二烯橡膠(SBR)、異戊二烯橡膠(IR)、丁二烯橡膠(BR)、(甲基)丙烯腈丁二烯橡膠(NBR)、聚胺甲酸酯、聚丙烯、(甲基)丙烯酸系寡聚物、(甲基)丙烯酸系聚合物、及聚矽氧樹脂等熱塑性高分子化合物。這些賦予可撓性之成分可單獨使用1種或可適當混合2種以上來使用。 The other components are not particularly limited, and examples thereof include components that impart flexibility. The components that impart flexibility are not particularly limited as long as they can impart flexibility to the layer containing the film, and examples thereof include the compound (A) of this embodiment, benzophenone,

Thermoplastic polymer compounds such as polyimide, polyamide imide, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), (meth)acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic oligomer, (meth)acrylic polymer, and polysilicone resin, excluding the compound (D), the acrylic compound (E) and the flux component (F). These components imparting flexibility may be used alone or in combination of two or more.

The film of this embodiment may also contain a silane coupling agent as another component for the purpose of improving the adhesion of the interface between the resin and the inorganic filler and improving the moisture absorption and heat resistance. Examples of the silane coupling agent include: vinyl trimethoxysilane, γ-methacryloyloxypropyl trimethoxysilane and other vinyl silane-based silane coupling agents; N-phenyl-3-aminopropyl trimethoxysilane and other phenylamino silane-based silane coupling agents; trimethoxyphenyl silane and other phenyl silane-based silane coupling agents; imidazole silane-based silane coupling agents. These silane coupling agents may be used alone or in combination of two or more.

When a silane coupling agent is used, its content is not particularly limited. From the perspective of improving moisture absorption and heat resistance and reducing volatility during flip chip mounting, it is preferably 0.05 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of compound (A).

The film of this embodiment may contain a wetting dispersant as another component for the purpose of improving the manufacturability of the laminate and the dispersibility of the filler. There is no particular limitation on the wetting dispersant as long as it is a wetting dispersant commonly used in coatings, etc. Examples include Disperbyk (registered trademark)-110 (trade name), Disperbyk (registered trademark)-111 (trade name), Disperbyk (registered trademark)-180 (trade name), Disperbyk (registered trademark)-161 (trade name), BYK-W996 (trade name), BYK-W9010 (trade name), and BYK-W903 (trade name) manufactured by BYK Japan. These wetting dispersants may be used alone or in combination of two or more.

When a wetting dispersant is used, its content is not particularly limited. From the perspective of improving the manufacturability of the laminate, it is preferably set to 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the inorganic filler (G). In addition, when two or more wetting dispersants are used in combination, their total amount should conform to the above ratio.

The film of this embodiment may contain various additives as other components for various purposes within the scope of not damaging the expected properties. The additives include, for example, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, levelers, brighteners, flame retardants, and ion scavengers. These additives may be used alone or in combination of two or more. There is no particular limitation on the photopolymerization initiator, and examples include, for example, alkyl phenyl ketone-based photopolymerization initiators, acyl phosphine oxide-based photopolymerization initiators, and diocene-based photopolymerization initiators.

In the film of this embodiment, the content of other additives is not particularly limited, and is usually 0.01 to 10 parts by mass relative to 100 parts by mass of compound (A).

The film of this embodiment is suitable for use as a pre-coated bottom filling material, so it is preferably in a semi-hardened state (B stage). The film in a semi-hardened state can obtain excellent low voids and chip adhesion. In this embodiment, the semi-hardened state (B stage) means that the components contained in the film have not yet begun to actively react (harden), but the film is in a dry state, that is, the state in which the solvent is evaporated by heating to the extent that there is no adhesion, and also includes the state in which the solvent is not heated and has not yet hardened but only evaporates. In this embodiment, the minimum melt viscosity of the semi-hardened state (B stage) is usually less than 50,000 Pa. s. In addition, the minimum melt viscosity can be measured using the method described in the embodiment described below.

The thickness of the film of this embodiment is not particularly limited. From the perspective of ensuring the filling of the bottom filling material between the connection terminals during installation, it is preferably greater than 10μm and less than 100μm, and more preferably greater than 10μm and less than 50μm.

[Thin film manufacturing method]

化合物(D)、丙烯基化合物(E)、助熔劑成分(F)、無機填充材(G)、氫過氧化物(H)、其它成分，其後，製成使這些成分溶解或分散於有機溶劑而成的清漆之形態，並將該清漆塗佈於支持體上以及進行乾燥來獲得。具體的製造方法可參考後述疊層體的製造方法及實施例。本實施形態之薄膜在乾燥後，可從支持體剝離後來使用，也可和支持體一起使用。 The film of the present embodiment is not particularly limited in its production method as long as it can obtain the above-mentioned composition. The film of the present embodiment can be produced by, for example, appropriately mixing the compound (A), the organic peroxide (B), and the imidazole compound (C), and appropriately mixing the benzophenone compound (B) as needed.

Compound (D), acrylic compound (E), flux component (F), inorganic filler (G), hydroperoxide (H), and other components are prepared, and then these components are dissolved or dispersed in an organic solvent to form a varnish, and the varnish is applied on a support and dried to obtain the film. The specific production method can refer to the production method and embodiment of the laminate described later. The film of this embodiment can be used after being peeled off from the support after drying, or it can be used together with the support.

There is no particular limitation on the organic solvent as long as it can properly dissolve or disperse the aforementioned components and does not damage the desired effect of the film of the present embodiment. Examples of organic solvents include: alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes referred to as "MEK"), and methyl isobutyl ketone; amides such as dimethylacetamide and dimethylformamide; aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used alone or in combination of two or more.

The support can be a known one without any particular limitation, and is preferably a resin film. Examples of resin films include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetyl acetate film. Among them, PET film is preferred.

[Layer]

The laminate of the present embodiment comprises: a supporting substrate, and a layer containing the film of the present embodiment laminated on the supporting substrate. Such a laminate is obtained by attaching the film of the present embodiment to the supporting substrate. The supporting substrate is not particularly limited, and a polymer film can be used. For example, the material of the polymer film includes a film containing at least one resin selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polybutylene, polybutadiene, polyurethane, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyethylene naphthalate, and polyester such as polybutylene terephthalate, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polyimide, and polyamide, and a release film formed by applying a release agent on the surface of these films. Among them, polyester, polyimide, and polyamide are preferred, and polyethylene terephthalate, which is a type of polyester, is more preferred.

There is no particular restriction on the thickness of the support substrate. Considering the manufacturability of the laminate, for example, the stability of the coating thickness when the thin film is coated on the support substrate and the transportability of the laminate, it is preferably 10~100μm. Considering the viewpoint of ensuring the yield when manufacturing the laminate, the lower limit of the thickness of the support substrate is preferably 12μm or more, preferably 25μm or more, and even more preferably 30μm or more. Considering that the support substrate will not ultimately exist as a component of the semiconductor device, but will be peeled off during the steps, and the viewpoint of the manufacturing cost of the laminate, the upper limit of the thickness of the support substrate is preferably 80μm or less, and even more preferably 50μm or less.

There is no particular limitation on the method of manufacturing a laminate of the present embodiment by forming a layer containing the thin film of the present embodiment on a supporting substrate (hereinafter also referred to as "thin film layer" for short). Such a manufacturing method can be exemplified by applying a varnish obtained by dissolving or dispersing the thin film of the present embodiment in an organic solvent on the surface of a supporting substrate, and heating and/or drying under reduced pressure to remove the solvent and harden the thin film of the present embodiment to form a thin film layer. There is no particular limitation on the drying conditions, and the drying is usually performed in such a manner that the content ratio of the organic solvent relative to the thin film layer becomes 10 parts by mass or less, preferably 5 parts by mass or less, relative to the total amount of the thin film layer (100 parts by mass). The conditions for achieving the drying can be appropriately adjusted depending on the type and amount of the organic solvent in the varnish. For example, when the varnish contains 10 to 120 parts by mass of methyl ethyl ketone relative to 100 parts by mass of compound (A), the standard is to dry for about 3 to 10 minutes under heating conditions of 90 to 160°C at 1 atmosphere.

[Semiconductor wafer with thin film layer, and semiconductor mounting substrate with thin film layer]

The semiconductor wafer with a thin film layer of the present embodiment comprises: a semiconductor wafer, and a stacking body of the present embodiment stacked on the semiconductor wafer, and the layer containing the thin film is stacked on the semiconductor wafer. In addition, the semiconductor mounting substrate with a thin film layer of the present embodiment comprises: a semiconductor mounting substrate, and a stacking body of the present embodiment stacked on the semiconductor mounting substrate, and the layer containing the thin film is stacked on the semiconductor mounting substrate.

There is no particular restriction on the method of manufacturing the semiconductor wafer with the thin film layer of the present embodiment. For example, it can be obtained by laminating the thin film layer of the stacked body of the present embodiment so that it faces the electrode-forming surface of the semiconductor wafer, that is, the surface to be bonded to the substrate. In addition, there is no particular restriction on the method of manufacturing the semiconductor mounting substrate with the thin film layer of the present embodiment. For example, it can be obtained by laminating the thin film layer of the stacked body of the present embodiment so that it faces the chip mounting side surface of the semiconductor mounting substrate.

There is no particular limitation on the method of bonding the stacked body of the present embodiment to a semiconductor wafer or a semiconductor mounting substrate, and a vacuum pressurized laminator can be appropriately used. At this time, it is preferable to pressurize and bond the stacked body of the present embodiment through an elastic body such as rubber. There is no particular limitation on the lamination conditions as long as they are the conditions commonly used by those having ordinary knowledge in the technical field to which the invention belongs. For example, the lamination can be carried out at a temperature of 50 to 140°C, with a contact pressure in the range of 1 to 11 kgf/ ^cm2 , and in a reduced pressure environment below 20 hPa. After the lamination step, the laminated body can also be smoothed by hot pressing using a metal plate. The above-mentioned lamination step and smoothing step can be continuously implemented using a commercially available vacuum pressure laminator. The stacked body attached to the semiconductor wafer or the semiconductor mounting substrate can be removed from the supporting substrate before the flip-chip mounting of the chip in any case.

[Semiconductor devices]

The semiconductor device of the present embodiment comprises: a semiconductor wafer with a thin film layer of the present embodiment and/or a semiconductor mounting substrate with a thin film layer of the present embodiment. The method of manufacturing the semiconductor device of the present embodiment is not particularly limited, and examples thereof include thinning the semiconductor wafer with a thin film layer of the present embodiment by means of grinding or the like, and singulating the wafer with a thin film layer by means of a slicing saw or the like to produce a chip with a thin film layer, which is then mounted on a semiconductor mounting substrate. Alternatively, the chip may be mounted on the semiconductor mounting substrate with a thin film layer of the present embodiment. The method of mounting a chip with a thin film layer on a semiconductor mounting substrate and the method of mounting a semiconductor chip on a semiconductor mounting substrate with a thin film layer can appropriately use a flip chip bonder corresponding to the hot pressing method. In addition, for convenience, the present embodiment is described in terms of the case where the chip is flip-chip mounted on a semiconductor mounting substrate, but the object for flip-chip mounting the chip and using the thin film of the present embodiment can also be an object other than a semiconductor mounting substrate. For example, the thin film of the present embodiment can also be used in the bonding portion between semiconductor wafers and chips when the chip is mounted on a semiconductor wafer, or in the bonding portion between chips of a chip stack body that implements chip-to-chip connection via TSV (Through Silicon Via), and the superiority brought by the present invention can be obtained in any occasion.

[Implementation example]

Hereinafter, the present embodiment will be described in more detail using examples and comparative examples. The present embodiment is not limited in any way by the following examples.

[Production of thin films and laminates]

(Implementation Example 1)

The following four compounds were used in combination as compound (A). Specifically, 38.47 parts by mass of a maleimide compound represented by the above formula (7) with n ³ being 14 (average value) (BMI-1000P (trade name), manufactured by K.I. Chemicals Co., Ltd.), 11.08 parts by mass (5.54 parts by mass in terms of non-volatile content) of a MEK solution of bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), manufactured by K.I. Chemicals Co., Ltd.) (non-volatile content 50%), 22.16 parts by mass (11.08 parts by mass as non-volatile components) of a MEK solution of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (BMI-80 (trade name), manufactured by K.I. Chemicals Co., Ltd.) (non-volatile components 50% by mass), and 64.16 parts by mass (44.91 parts by mass as non-volatile components) of a MEK solution containing a maleimide compound in which all ^R13 in the above formula (9) are hydrogen atoms (MIR-3000-70MT (trade name), manufactured by Nippon Kayaku Co., Ltd., non-volatile components 70% by mass).

化合物(D)之P-d型苯并

(四國化成工業(股)製)之MEK溶液(非揮發成分50質量%)76.94質量份(以非揮發成分換算計38.47質量份)、作為助熔劑成分(F)之松香改性馬來酸樹脂(MALKYDNo32(商品名)，荒川化學工業(股)製)之MEK溶液(非揮發成分50質量%)55.38質量份(以非揮發成分換算計27.69質量份)、作為無機填充材(G)之漿體二氧化矽(YA050C-MJE，固體成分50%，平均粒徑：50nm，Admatechs(股)製)276.94質量份(以非揮發成分換算計138.47質量份)、作為有機過氧化物(B)之下式(1-1)表示之有機過氧化物(過氧化二異丙苯，KISHIDA化學(股)製)1.55質量份、及作為咪唑化合物(C)之下式(5-1)表示之咪唑化合物(2E4MZ(商品名)，四國化成工業(股)製)1.38質量份和上述4種化合物(A)混合，並使用高速攪拌裝置攪拌40分鐘，獲得清漆。 Also, benzo

Compound (D) Pd-type benzo

76.94 parts by mass (38.47 parts by mass as non-volatile component conversion) of MEK solution (50% by mass of non-volatile component) of (manufactured by Shikoku Chemical Industries, Ltd.), 55.38 parts by mass (27.69 parts by mass as non-volatile component conversion) of rosin-modified maleic acid resin (MALKYD No32 (trade name), manufactured by Arakawa Chemical Industries, Ltd.) as flux component (F), slurry silica (YA050C-MJE, solid content 50%, average particle size: 50nm) as inorganic filler (G) m, manufactured by Admatechs Co., Ltd.) 276.94 parts by mass (138.47 parts by mass as non-volatile components), 1.55 parts by mass of an organic peroxide represented by the following formula (1-1) as an organic peroxide (diisopropyl peroxide, manufactured by Kishida Chemical Co., Ltd.), and 1.38 parts by mass of an imidazole compound represented by the following formula (5-1) as an imidazole compound (C) were mixed with the above four compounds (A), and stirred for 40 minutes using a high-speed stirring device to obtain a varnish.

The obtained varnish was applied to a 38μm thick polyethylene terephthalate film (TR1-38 (trade name), manufactured by UNITIKA Co., Ltd.) with a release agent on the surface, and dried at 100°C for 5 minutes to obtain a laminate with a film layer thickness of 30μm. In addition, the content of compound (A) in the film was calculated from the mass of the film to be 32.5 mass %.

(Example 2)

The blending amount of 2E4MZ as the imidazole compound (C) was changed to 4.15 parts by mass. The varnish was prepared in the same manner as in Example 1, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 3)

As for the imidazole compound (C), 2.17 parts by mass of an imidazole compound represented by the following formula (5-2) (1B2MZ (trade name), manufactured by Shikoku Chemical Industries, Ltd.) was used to replace 2E4MZ. In addition, a varnish was prepared in the same manner as in Example 1, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 4)

The blending amount of 1B2MZ as the imidazole compound (C) was changed to 6.51 parts by mass. The varnish was prepared in the same manner as in Example 3, and a laminate having a film layer thickness of 30 μm was obtained.

(Example 5)

As for the imidazole compound (C), 1.20 parts by mass of an imidazole compound represented by the following formula (5-3) (1,2-DMZ (trade name), manufactured by Shikoku Chemical Industries, Ltd.) was used to replace 2E4MZ. In addition, a varnish was prepared in the same manner as in Example 1, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 6)

The blending amount of 1,2-DMZ as the imidazole compound (C) was changed to 3.63 parts by mass. The varnish was prepared in the same manner as in Example 5, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 7)

The blending amount of diisopropylbenzene peroxide as the organic peroxide (B) was changed to 6.92 parts by mass. The varnish was prepared in the same manner as in Example 2, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 8)

As for the organic peroxide (B), 1.55 parts by weight of an organic peroxide represented by the following formula (2-1) (PERBUTYL P (trade name), manufactured by NOF Corporation) was used to replace diisopropylbenzene peroxide. In addition, a varnish was prepared in the same manner as in Example 2, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 9)

The blending amount of PERBUTYL P as the organic peroxide (B) was changed to 6.92 parts by mass. The varnish was prepared in the same manner as in Example 8, and a laminate having a film layer thickness of 30 μm was obtained.

(Example 10)

As for the organic peroxide (B), 1.55 parts by mass of an organic peroxide represented by the following formula (2-2) (PERHEXA V (trade name), manufactured by NOF Corporation) was used to replace diisopropylbenzene peroxide. In addition, a varnish was prepared in the same manner as in Example 2, and a laminate having a film layer thickness of 30 μm was obtained.

(Implementation Example 11)

The blending amount of PERHEXA V as the organic peroxide (B) was changed to 6.92 parts by mass. The varnish was prepared in the same manner as in Example 10, and a laminate having a film layer thickness of 30 μm was obtained.

(Example 12)

Among the above four compounds (A), a maleimide compound represented by the above formula (6) and having ⁿ² of 1 to 3 (BMI-2300 (trade name), manufactured by Yamato Chemical Industries, Ltd.) was used in an amount of 14.29 parts by mass in place of MIR-3000-70MT, and the blending amount of BMI-70 was changed to 23.62 parts by mass (calculated as non-volatile components), and the blending amount of BMI-80 was changed to 23.62 parts by mass (calculated as non-volatile components). In addition, a varnish was prepared in the same manner as in Example 2, and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 1)

Except that 2E4MZ was not used as the imidazole compound (C), a varnish was prepared in the same manner as in Example 1, and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 2)

The varnish was prepared in the same manner as in Example 1 except that 2.95 parts by mass of an imidazole compound represented by the following formula (5'-1) (1B2PZ (trade name), manufactured by Shikoku Chemical Industries, Ltd.) was used to replace 2E4MZ as the imidazole compound (C), and a laminate having a film layer thickness of 30 μm was obtained.

[Chemistry 88]

(Comparison Example 3)

The varnish was prepared in the same manner as in Comparative Example 2 except that the blending amount of 1B2PZ as the imidazole compound (C) was changed to 8.86 parts by mass, and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 4)

The varnish was prepared in the same manner as in Example 1 except that 1.99 parts by mass of an imidazole compound represented by the following formula (5'-2) (2P4MZ (trade name), manufactured by Shikoku Chemical Industries, Ltd.) was used to replace 2E4MZ as the imidazole compound (C), and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 5)

The varnish was prepared in the same manner as in Comparative Example 4 except that the blending amount of 2P4MZ as the imidazole compound (C) was changed to 5.98 parts by mass, and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 6)

The varnish was prepared in the same manner as in Example 1 except that 3.74 parts by mass of an imidazole compound represented by the following formula (5'-3) (TPIZ (trade name), manufactured by Tokyo Chemical Industry Co., Ltd.) was used to replace 2E4MZ as the imidazole compound (C), and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 7)

The varnish was prepared in the same manner as in Comparative Example 6 except that the blending amount of TPIZ as the imidazole compound (C) was changed to 11.20 parts by mass, and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 8)

The varnish was prepared in the same manner as in Example 2 except that 1.55 parts by mass of an organic peroxide represented by the following formula (1-4) (PERBUTYL D (trade name), manufactured by NOF Corporation) was used to replace diisopropylbenzene peroxide as the organic peroxide (B), and a laminate having a film layer thickness of 30 μm was obtained.

[Chemistry 91]

(Comparative Example 9)

1.55 parts by mass of hydroperoxide (PERMENTA H (trade name), manufactured by NOF Corporation) represented by the following formula (1-5) was used to replace diisopropylbenzene peroxide. The varnish was prepared in the same manner as in Example 2, and a laminate having a film layer thickness of 30 μm was obtained.

(Comparison Example 10)

Except that diisopropylbenzene peroxide was not used as the organic peroxide (B), a varnish was prepared in the same manner as in Example 2, and a laminate having a film layer thickness of 30 μm was obtained.

[Evaluation of the stack]

(1) Storage stability of varnish

The viscosity (a) of the varnish obtained in Examples 1 to 12 and Comparative Examples 1 to 10 was measured using a B-type viscometer (manufactured by Tokyo Instruments Co., Ltd.) at 25°C, and the viscosity (b) after being placed in a sealed container at 25°C for one week was measured using a B-type viscometer. The viscosity change rate after one week was calculated using the following formula. When the viscosity change rate was less than 10%, it was recorded as AA, when it was 10% or more and less than 20%, it was recorded as A, when it was 20% or more and less than 40%, it was recorded as B, when it was 40% or more, it was recorded as C, and when gelation of the varnish was observed during the preparation of the varnish, it was recorded as D. The results are shown in Tables 1 to 2.

Viscosity change rate = [｜Viscosity (b) - Viscosity (a)｜/Viscosity (a)] × 100

(2)Flexibility

The laminated bodies obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were cut into strips of 5 cm × 10 cm, and then rolled onto a metal tube with a predetermined outer diameter at room temperature with the polyethylene terephthalate film supporting the substrate on the inner side, and then returned after 5 seconds. After repeating this operation 10 times, the resin composition layer was visually checked for cracks, and the flexibility was evaluated. The outer diameter of the minimum metal tube in which no cracks were observed in the resin composition layer was recorded as AA when it was less than 10 mm, A when it was greater than 10 mm and less than 20 mm, B when it was greater than 20 mm and less than 60 mm, and C when it was greater than 60 mm. The results are shown in Tables 1 to 2.

(3) Flux activity

The resin powder obtained by crushing the thin film layer obtained in Examples 1 to 12 and Comparative Examples 1 to 10 was spread on the glossy surface of an electrolytic copper foil (3EC-III (trade name), manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm, and a solder ball (ECO SOLDER (registered trademark) BALL M705 (trade name), Sn-3.0Ag-0.5Cu alloy, manufactured by Senju Metal Industries, Ltd.) with a diameter of 0.5 mm was placed. It was heated on a heating plate maintained at 235°C for 1 minute to melt the solder on the copper foil, and then cooled to room temperature. The flux activity was evaluated by measuring the contact angle of the solder ball that was wetted and spread on the copper foil. The contact angle of the solder ball is determined by using a digital microscope (KH-7700 (trade name), manufactured by HIROX Co., Ltd.) to obtain the radius (c) and height (d) of the solder ball that is melted and wetted on the copper foil, and the contact angle is calculated using the following formula.

Contact angle of solder ball = 2arctan[(d)/(c)]

When the contact angle of the solder ball is less than 1.60 radians, it is recorded as AA; when it is greater than 1.60 radians and less than 2.00 radians, it is recorded as A; when it is greater than 2.00 radians and less than 2.20 radians, it is recorded as B; when it is greater than 2.20 radians, it is recorded as C. The results are shown in Tables 1 and 2.

(4) Hardening

The resin powder obtained by crushing the thin film layer in the laminate obtained in Examples 1 to 12 and Comparative Examples 1 to 10 was measured for heat release in the range of 30°C to 350°C at a temperature increase rate of 10°C/min using a differential scanning calorimeter (Q100 (trade name), manufactured by TA Instruments). When the heat release (W/g) at 145°C is 0.04W/g or more, it is recorded as AA, when it is 0.03W/g or more and less than 0.04W/g, it is recorded as A, when it is 0.02W/g or more and less than 0.03W/g, it is recorded as B, and when it is less than 0.02W/g, it is recorded as C. The results are shown in Tables 1 to 2.

(5) Gap

After the laminated bodies obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were cut into 8 mm × 8 mm squares and laminated on an evaluation substrate, a semiconductor chip having a Cu column composed of copper and solder at the electrode was thermally pressed and mounted using a flip chip bonder (LFB-2301 (trade name), manufactured by Shinkawa Co., Ltd.) at a stage temperature of 70°C, a bonding head temperature of 260°C, a load of 50 N, and a time of 6 seconds. The mounted samples were checked for voids in the thin film layer within the range of the semiconductor chip mounting portion using an ultrasonic flaw detection imaging device (μ-SDS (trade name), manufactured by KRAUTKRAMER JAPAN Co., Ltd.). When the void ratio is less than 10%, it is recorded as AA; when it is less than 15% and 10% or more, it is recorded as A; when it is less than 30% and 15% or more, it is recorded as B; when it is more than 30%, it is recorded as C. The results are shown in Tables 1 and 2.

(6) Minimum melt viscosity

1 g of the resin powder obtained by crushing the film layer obtained in Examples 1 to 12 and Comparative Examples 1 to 10 was weighed and formed into a tablet with a diameter of 25 mm and a thickness of 1.5 mm using a tablet former (SSP-10A (trade name), manufactured by Shimadzu Corporation) at a pressure of 20 kN and a time of 5 minutes. The viscosity was measured in the range of 40°C to 260°C using a rheometer (ARES-G2 (trade name), manufactured by TA Instruments) at a temperature increase rate of 10°C/min. The lowest melt viscosity was recorded as AA when it was 5000 Pa.s or more and less than 15000 Pa.s, and the lowest melt viscosity was recorded as AA when it was 15000 Pa.s or more and less than 20000 Pa.s or 1000 Pa.s. When the minimum melt viscosity is above 20000Pa.s and below 25000Pa.s or above 100Pa.s and below 1000Pa.s, it is recorded as A; when the minimum melt viscosity is above 25000Pa.s or below 100Pa.s, it is recorded as B; when the minimum melt viscosity is above 25000Pa.s or below 100Pa.s, it is recorded as C. The results are shown in Tables 1~2.

[Table 2]

This application is based on a Japanese patent application filed on June 28, 2019 (Japanese Patent Application No. 2019-122352), and its contents are incorporated herein by reference.

[Industrial applicability]

The film of this embodiment is suitable as a pre-coating bottom filling material because of its excellent balance of various physical properties such as storage stability, flexibility, flux activity, curability, low voids, and melt viscosity. In addition, the film of this embodiment has excellent flux activity, so it can be used in the stacked body obtained by bonding the chip to the substrate, bonding the chip to the semiconductor wafer, and bonding the chip to the chip to provide high reliability that can withstand long-term use.

Claims (27)

A pre-coated bottom filling material in the form of a film, the film comprising: a compound (A) comprising at least one selected from the group consisting of maleimide compounds and oxadiazine compounds, an organic peroxide (B) comprising at least one selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2), and an imidazole compound (C) represented by formula (5); the content of the compound (A) in the film is 10 mass % or more and 60 mass % or less, the content of the organic peroxide (B) is 0.01 mass part or more and 15 mass parts or less relative to 100 mass parts of the compound (A), and the content of the imidazole compound (C) is 10 mass parts or less relative to 100 mass parts of the compound (A);

In formula (1), R ¹ each independently represents a hydrogen atom, a methyl group, or an ethyl group;

In formula (2), ^R2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and ^X1 represents a group represented by the following formula (3) or (4);

In formula (3), R ³ represents a hydrogen atom, a methyl group, or an ethyl group, R ⁴ represents an alkylene group having 1 to 3 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

In formula (4), R ⁶ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and X ² represents a group represented by the following general formulas (a) to (c);

In formula (c), n ¹ represents an integer greater than or equal to 1 and less than or equal to 5;

In formula (5), ^R7 represents a methyl group or an ethyl group, ^R8 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and ^R9 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group. The pre-coated bottom filling material in the form of a thin film as claimed in claim 1, wherein the compound (A) comprises a compound selected from 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimalimidamide, N,N'-1,4 - at least one selected from the group consisting of phenylene dimaleenide, N-phenylmaleimide, a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), a maleimide compound represented by the following formula (9), and a bismaleimide compound having a constituent unit represented by the following formula (10) and maleimide groups at both ends;

In formula (6), R ¹⁰ each independently represents a hydrogen atom or a methyl group, and n ² represents an integer greater than 1;

In formula (7), n ³ represents an integer greater than or equal to 1 and less than or equal to 30;

In formula (8), R ¹¹ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ¹² each independently represents a hydrogen atom, or a methyl group;

In formula (9), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer of 1 to 10;

In formula (10), ^R14 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; ^R15 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; ^R16 each independently represents a hydrogen atom, a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms; and ⁿ⁵ represents an integer of 1 to 10. A pre-coated bottom filling material in the form of a thin film as claimed in claim 2, wherein the compound (A) comprises at least one selected from the group consisting of 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane, a maleimide compound represented by the formula (6), a maleimide compound represented by the formula (7), a maleimide compound represented by the formula (8), a maleimide compound represented by the formula (9), and a bismaleimide compound containing a constituent unit represented by the formula (10) and maleimide groups at both ends. The pre-coated bottom filling material in the form of a thin film as claimed in claim 1, wherein the organic peroxide (B) comprises at least one selected from the group consisting of diisopropylbenzene peroxide, 4,4-di(tertiary butylperoxy) valerate, di(2-tertiary butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)-3-hexyne, and 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane. The pre-coated bottom filling material in the form of a thin film as claimed in claim 1, wherein the imidazole compound (C) is an imidazole compound represented by the following formula (11);

In formula (11), R ¹⁷ represents a methyl group or an ethyl group, R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and R ¹⁹ represents a hydrogen atom or a methyl group. The pre-coated bottom filling material in the form of a thin film as claimed in claim 5, wherein the imidazole compound (C) is an imidazole compound represented by the following formula (12);

In formula (12), ^R20 represents a methyl group or an ethyl group, ^R21 represents a hydrogen atom, a methyl group, an ethyl group or a benzyl group, and ^R22 represents a hydrogen atom or a methyl group. A pre-coated bottom filling material in the form of a thin film as claimed in claim 5, wherein the imidazole compound (C) comprises at least one selected from the group consisting of 1-benzyl-2-methylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. The pre-coated bottom filling material in the form of a thin film as claimed in claim 1 further contains benzo(13), (14), (15), and (16) represented by the following formulas:

Compound (D);

In formula (13), ^R23 each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, ^R24 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a 1-4 valent organic group represented by the following general formulae (d) to (w), and ⁿ⁵ represents an integer of 1 to 4;

In formula (14), ^R25 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; ^R26 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a 1-4 valent organic group represented by the following general formulas (d) to (r); and ⁿ⁶ represents an integer of 1 to 4;

In formula (15), R ²⁷ represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent;

In formula (16), R ²⁸ represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent;

In formulae (d) to (w), ^Ra represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and ^Rb represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group. The pre-coated bottom filling material in the form of a thin film as claimed in claim 8, wherein the benzo

The compound (D) comprises at least one selected from the group consisting of compounds represented by the following formula (17) and the following formula (18);

In formula (17), ^R29 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; ^R30 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; ^X3 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula " _-SO2- ", a group represented by the formula "-CO-", an oxygen atom, or a single bond;

In formula (18), R ³¹ each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; R ³² each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group; X ⁴ represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO ₂ -", a group represented by the formula "-CO-", an oxygen atom, or a single bond;

In formula (19), Y is an alkylene group or a alkyl group having 6 or more and 30 or less carbon atoms and having an aromatic ring, and ⁿ⁷ represents an integer of 0 or more. The pre-coated bottom filling material in the form of a thin film as claimed in claim 8, wherein the benzo

Compound (D) comprises at least one selected from the group consisting of a compound represented by the following formula (20), a compound represented by the following formula (21), a compound represented by the following formula (22), a compound represented by the following formula (23), a compound represented by the following formula (24), and a compound represented by the following formula (25);

In formula (22), R ³³ each independently represents a hydrogen atom or a carbon number 1 to 4 alkyl group;

The pre-coated bottom filling material in the form of a thin film as claimed in claim 8, wherein the benzo

The content of the compound (D) is 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the compound (A). The pre-coated bottom filling material in the form of a thin film as in claim 1 further contains an acrylic compound (E). The pre-coated bottom filling material in the form of a thin film as claimed in claim 12, wherein the content of the acrylic compound (E) is 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A). The pre-coated bottom filling material in the form of a thin film as in claim 1 further contains a flux component (F). The pre-coated bottom filling material in the form of a thin film as claimed in claim 14, wherein the content of the flux component (F) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the compound (A). The pre-coated bottom filling material in the form of a thin film as in claim 1 further contains an inorganic filler (G). A pre-coated bottom filling material in the form of a thin film as claimed in claim 16, wherein the average particle size of the inorganic filler (G) is less than 3 μm. A pre-coated bottom filling material in a thin film form as claimed in claim 16, wherein the inorganic filler (G) comprises at least one selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide. The pre-coated bottom filling material in the form of a thin film as claimed in claim 16, wherein the content of the inorganic filler (G) is less than 300 parts by mass relative to 100 parts by mass of the compound (A). The pre-coated bottom filling material in the form of a thin film as in claim 1 further contains hydroperoxide (H). The pre-coated bottom filling material in the form of a thin film as claimed in claim 20, wherein the content of the hydroperoxide (H) is less than 10 parts by mass relative to 100 parts by mass of the total amount of the compound (A). The pre-coated bottom filling material in the form of a thin film as in claim 1 has a thickness of more than 10μm and less than 100μm. A laminated body comprising: a supporting substrate, and a layer of a pre-coated bottom filling material in the form of a thin film as described in any one of claims 1 to 22 laminated on the supporting substrate. A semiconductor wafer with a pre-coated bottom filling material layer, comprising: a semiconductor wafer, and a stacked body as claimed in claim 23 stacked on the semiconductor wafer; and the layer containing the pre-coated bottom filling material in a thin film form is stacked on the semiconductor wafer. A semiconductor mounting substrate with a pre-coated bottom filling material layer, comprising: a semiconductor mounting substrate, and a stacked body as claimed in claim 23 stacked on the semiconductor mounting substrate; and the layer containing the pre-coated bottom filling material in a thin film form is stacked on the semiconductor mounting substrate. A semiconductor device having a semiconductor wafer with a pre-coated bottom filling material layer as in claim 24. A semiconductor device having a semiconductor mounting substrate with a pre-coated bottom filling material layer as in claim 25.